Process of producing an antiknock compound



Feb. 9, 1932. H. K. lHRlG PROCESS OF PRODUCING AN ANTIKNOCK COMPOUND Filed June 15, 1927 VBR@ Parental Feb. 9, 1932 UNITED STATES PATENT OFFICE .llipllcation Bled .Tune 15, 1927. Serial lo. 199,119.

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Certain crude petroleums contain large` quantities of aromatic hydrocarbons, and it is with these that this process deals primarily. These aromatic hydrocarbons are objectionable in kerosene and are eliminated along with other impurities by reason of their solubility in a polar solvent, such as liquid sul hur dioxide. These impurities, together wit the polar solvent, are concentrated in an extract which may be separated from the insoluble hydrocarbons, which are termed ralinat, or refined petroleum products. It has been found that this extract, which has heretofore had a value about the same as fuel oil, may now be used as the starting point for the production of this compound, which, when mixed with gasoline, will produce an anti-knock motor fuel.

The principal object of this invention is, therefore, to produce a cheap non-poisonous and non-metallic anti-knock compound or mixture, which, when added to a low compression engine fuel, will produce a fuel that will meet the desired requirements.

This invention relates generally to the treatment of hydrocarbon materials with a polar solvent to obtain an extract consisting of aromatic, hydroaromatic and unsaturated hydrocarbons, concentrated in a relatively small volume; treating said extract with a suitable reagent such as 93% sulphuric acid for the removal of the unsaturated hydrocarbons, thereby leaving a remainder, comprising a mixture of aromatic, hydroaromatic m and partially hydrogenated aromatic compounds; nitrating said remainder or lany distillate fraction thereof; reducing said nitrated remainder; and subjecting it to steam distillation and-extraction with a suitable solvent to obtain a hydrogenated nitrogen hydrocarbon mixture. v

The accompanying How sheet diagrammatically illustrates my process.

My invention more in detail now will be fully disclosed:

First, as to the preparation of the extract:

A number of crude oils are known to contain hydrocarbons other than the saturated straight chain hydrocarbons. These h drocarbons may be classified as unsaturate hy- 65 droaromatic, vand aromatic hydrocarbons. Sometimes, hydroaromatic hydrocarbons are known as naphthenes, or hydrocarbons of the general type CnHZn, while the aromatic h drocarbons have the general formula Gn n.

In refining of oils other than those c ontainingthe first type or saturated straight chain hydrocarbons, there is difficulty using the ordinary methods of refining. In general,'these latter types of hydrocarbons, or 75 unsaturated, hydro-aromatic andf aromatic hydrocarbons, can be called polar compounds, as differentiated from the saturated or non-polar hydrocarbons. The fully hydrogenated aromatic compounds are mid- ,9 way between the non-polar and polar types.

In order to separate polar hydrocarbons from non-polar hydrocarbons, it is necessary to employ some means other than distillation. One of these means is the extraction with a polar solvent; the polar hydrocarbons going into solution in the polar solvent, and the non-polar hydrocarbons remaining behind as a separate layer. Such polar solvents are liquid sulphur dioxide, 9 liquid ammonia, or liquid hydrochloric acid. These compounds are solvents at ordinary temperatures and pressures, and hence can be readily removed after the extraction has been made, and then can be used for further treatment by reason of the continuous cycle.

The polar solvent most used in petroleum refining is liquid sulphur dioxide, because l of its cheapness and relative ease of liquefaction. In using liquid sulphur dioxide, the hydrocarbon material is agitated with liquid sulphur dioxide at 0 F. and 1 poundv gauge pressure. This may be done either in batches or continuousl by having the liquid sulphur dioxide ow countercurrently with the hydrocarbon material. After the liquid sulphur dioxide has become thoroughly mixed in intimate `contact with the hydrocarbon material, the mixture is allowed to settle. Two layers are observed; a top layer, which consists of the non-polar type of hydrocarbon, relatively free of sulphur dioxide; and a lower layer, composed of a solution of the olar hydrocarbons, other impurities and the iquid sulphur dioxide. The lower layer, which is the extract, is drawn off and the sulphur dioxide evaporated for further use in the cycle. The upper layer is called rafinat, and consists of the non-polar hydrocarbons and is used either as such or given appropriate, additional refining treatment to make the high quality refined oil products. The extract, which is the starting point of I this process, consists of unsaturated, hy-

droaromatic and aromatic hydrocarbons, concentrated in a relatively small volume. This material is therefore a valuable source for the production of derivatives of the above mentioned hydrocarbons concentrated in it. In preparing the extract, the hydrocarbon material is chosen of appropriate boiling range to make the desired derivative. In the refining of kerosene, the starting materialis called kerosene extract, while in the refining of cracked gasoline or ressure distillate, the material is known as pressure distillate extract.

Any hydrocarbon material may be treated with the polar solvent metioned above and the extract utilized to give the corresponding derivatives when treated according to description submitted herein.

For an example of actual operation, which is not to be construed in any way as a limitation, the following run was made:

About 500 allons of ressure distillate from the crac ing of California petroleum was treated with liquid sulphur dioxide, 50% by volume', 0 F., by exhaustive extraction, from which was obtained 62.36% of ratfinat, or non-polar hydrocarbon, and 35.71% was recovered as extract of polar hydrocarbon. This extract has a gravity of 31.4 A. P. I. and F., initial boiling point of 176 F. and an end point of 546 F. 175 gallons of this extract was thenwashed with water to free it from the sulphur dioxide and was then treated with 43 gallons of 93% sulphuric acid in six batches, drawing oif the sludge each time which contains the bulk of the unsaturated hydrocarbons soluble therein, such as oleiines, some of the olefines being polymerized and remain in the insoluble portion of the' mixture. The hydrocarbon mixture was neutralized and washed and then distilled with re and steam to remove the polymerized compound containing hydroaromatic, aromatic and polymerized oleinic hydrocarbons. The distillate after separation from the steam condensate was fractionated in a 15 gallon still with a 10 foot tower, from which a cut was made between the range ofV 370 to 380 F.' This fraction was nitrated with an equal volume of Iconcentrated nitric acid and one of concentrated sulphuric acid and a liquid nitro compound or mixture o compounds was obtained. No attempt was made to purifythis product but it was simply washed with water and then reduced. The reduction was accomplished by treating 200 grams with 400 grams of iron filings, 40 Cs. of concentrated hydrochloric acid and 30 Cs. of water, the acid being added slowly, r

of hydrogenated nitrogen hydrocarbons wasa brown liquid, soluble in hydrochloric acid and gave a marked reaction with acetyl chloride.

The product obtained from this particular run was mixed in small portions with low compression fuel such as kerosene or gasoline and it was found to produce an excellent anti-detonating motor fuel.

Fractions may be taken over a range from to 550 F. according tothe facility with which they may be nitrate'd, and various aromatic hydrocarbons which are amino derivatives are produced. While this process is designed to so treat the extract as to pro- -duce a mixture of hydrogenated nitrogen hydrocarbons, among which the aromatic amines have been identified, it should be apparent that these amines may be separated if desired. This mixture need not be further treated or purified as it etliciently accomplishes the purpose for which it is pro,- duced.

What I claim is:

1.v The method of producing aromatic hydrocarbon derivatives, which comprises treating a hydrocarbon material with a polar solvent to form an extract soluble therein, in which are concentrated the aromatic, hydroaromatic and unsaturated compounds separating from said extract the unsaturated compounds; and treating a remainder of said extract to produce a mixture of aromatic amines.

2. The method of producing a hydrocarbon mixture, containing aromatic a.mines,'which comprises treatinga hydrocarbon material with a polar solvent to form an extract soluble therein, in which are concentrated the aromatic, hydroaromatic and unsaturated compounds; separating from said extract the unsaturated compounds; nitrating a remainder of said extract; and treating the nitro compound mixture to produce the desired mixture of aromatic amines.-

`3. The method of producing a hydrocarbon mixture, containing aromatic amines, which comprises treating a hydrocarbon material with a polar solvent to form an extract soluble therein, in which are concentrated the aromatic, hydroaromatic and unsaturated compounds, separating from said extract the unsaturated compounds; nitrating a remainder of said extract; reducing the nitro compound mixture; and treating to obtain the desired mixture of aromatic amines.

4. The method of producing a hydrocarbon mixture, containing aromatic amines, which comprises treating a hydrocarbon material with a polar solvent to form an extract soluble therein, in which are concentrated the aromatic, hydroaromatic and unsaturated compounds; separating from said extract the unsaturated compounds; nitrating a remainder of said extract; reducingr the nitro compound mixture; purifying by distillation; and treating to obtain the desired mixture of aromatic` amines.

5. The method of producing a hydrocarbon mixture, containing aromatic amines, which comprises treating a hydrocarbon material with a polar solvent to form an extract soluble therein, in which are concentrated the aroinatic, hydroaromatic and unsaturated compounds; separating from said extract the unsaturated compounds: nitrating a remainder of said extract; reducing the nitro compound mixture; purifying by steam distillation and extracting an additional portion of the desired mixture of aromatic amines with a suitable solvent from the steam condensate.

6. A process of producing aromatic amines, which comprises treating a hydrocarbon matcrial with a polar solvent to form an extract soluble therein, in which are concentrated the aromatic, hydroaromatic and unsaturated compounds; separating from said eX- tract the unsaturated compounds; nitrating a remainder of said extract; reducing the nitro compound mixture; and treating to separate the particular aromatic amine desired.

i'. A method of producing a mixture containing aromatic amines, which comprises treating a hydrocarbon material with a polar solvent to form an extract soluble therein, in `which are concentrated the aromatic, hydroarornatic and unsaturated compounds; sepacert-ain unsaturated compounds, removing the acid and dissolved compounds, fractions-ting the remaining compounds, nitrating a selected fraction, reducing the nitrated fraction, and treating the reduced fraction to separate a portion containing aromatic amino derivatives.

9. A processof treating a mixture of hydrocarbons containing olefines, hydroaromatlcs and aromatics which comprisesi adding 93% sulphuric acid to said mixture to dissolve out certain unsaturated compounds, removlng the acid and dissolved compounds, fractionating the remaining compounds, nitrating a selected fraction, reducing the nitrated fraction, and treating the reduced fraction to separate a portion containing aromatic amino derivatives.

10. process of treating a mixture of hydrocarbons containing olenes, hydroaromatics and aromatics which comprises: adding sulphuric acid to said mixture to dissolve put certain unsaturated compounds, removlng the acid and'dissolved compounds, fractionating the remaining compounds, nitrating a selected fraction having a boiling range from 100 F. to 550 F., reducing the nitrated vfraction, and treating the reduced fraction to .separate a portion containing aromatic ammo derivatives. ,y

11. A process of treating a mixture of hydrocarbons containing olefines, hydroaromatics and aromatica which comprises: adding sulphuric acid to said mixture to dissolve out certain unsaturated compounds, removlng the acid and l'lissolved compounds, fractlonating the remaining compounds, nitrating a selected fraction having a boiling range from 370 F. to 380 F., reducing the nitrated fraction, and treating the reduced fraction to separate a portion containing aromatic amino derivatives.

12. A process of treating a mixture of hydrocarbons containing oleines, hydroaromatics and aromatics which comprises: adding sulphuric acid to said mixture to dissolve out certain unsaturated compounds, removing the acid and dissolved compounds, fractionating the remaining compounds, nitrating a. selected fraction, reducing the nitrated fract1on, distilling the reduced fracton with steam, and extracting that part of said fraction soluble in the steam condensate with a suitable solvent.

ditional portion of v .13.. A process of treatin a mixture of hydrocarbons containing ole nes, h droaromatics and aromatcs which comprises: adding sulphuric acid to said mixture to dissolve out certain unsaturated compounds, removing the acid and dissolved compounds, frictionating the remaining compounds, nitrating ,a selected fraction, reducing the nitrated fraction,- distilling the :reduced fraction with steam, and extracting that part of .said fraction soluble in the steam condensate with gasoline.

HARRY KARL IHRIG. 

